200300406 A7 B7 五、發明説明（） 發明之技術領域 本發明係有關丙烯酸的製造製程所產生的廢液中除去 金屬的方法。 先行技術 有關丙烯酸的製造，作爲催化劑的含有氧化鉬成分的 固體催化劑，多數使用銅化合物作爲助劑’丙烯酸的製造 製程所產生的廢液含上述的金屬。 一般，丙烯酸的製造製程所產生的廢液除去金屬的方 法，有如以下的方法。（1)調整廢液的pH ，加入析出劑， 其次加入凝結劑，沈降的固體成分以壓濾器或離心機分離 的方法，（2)更以吸附劑、離子交樹脂的組合除去金屬的方 法。 一方面，丙烯酸的製造製程所產生的廢液，由於含醋 酸或醛類等的種種有機物質，此等有機物質採用以濕式燃 燒或濕式氧化變換爲無害的碳酸氣、水等的方法。但是， 雖將有機物質無害化，廢液中含有的金屬原樣混入處理液 的廢水中。 如上述向來的廢液中除去金屬的方法，由於並非以濕 式燃燒、濕式氧化處理的廢水爲對象的技巧，對廢水雖使 用上述方法，基於廢水特有的性狀，對除去金屬的效率下 降，具體的如使用的藥劑量或殘留的金屬濃度，與通常比 較有增加的問題點。 又，「濕式燃燒」係廢液以燃燒處理的同時，由燃燒 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) 、言 經濟部智慧財產局員工消費合作社印製200300406 A7 B7 V. Description of the invention () Technical field of the invention The present invention relates to a method for removing metal from waste liquid produced in the manufacturing process of acrylic acid. Prior art Regarding the production of acrylic acid, as a solid catalyst containing a molybdenum oxide component as a catalyst, a copper compound is mostly used as an auxiliary agent. The waste liquid produced in the production process of acrylic acid contains the above-mentioned metals. Generally, the method for removing metal from the waste liquid produced in the acrylic acid manufacturing process is as follows. (1) The method of adjusting the pH of the waste liquid, adding a precipitating agent, followed by adding a coagulant, and the sedimented solid components are separated by a filter or a centrifuge, and (2) a method of removing metal by a combination of an adsorbent and an ionomer resin. On the one hand, the waste liquid produced in the manufacturing process of acrylic acid contains various organic substances such as acetic acid and aldehydes, and these organic substances are converted into harmless carbon dioxide gas and water by wet combustion or wet oxidation. However, although the organic matter is rendered harmless, the metal contained in the waste liquid is mixed into the wastewater of the treatment liquid as it is. As described above, the conventional method for removing metals from waste liquid is not a technique targeted at the waste water of wet combustion and wet oxidation treatment. Although the above method is used for waste water, the efficiency of removing metal is reduced based on the characteristics of the waste water. Specific issues such as the dosage of the drug used or the residual metal concentration have increased points compared to usual. In addition, "wet combustion" means that when the waste liquid is burned, the size of the paper is applied to the Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the precautions on the back before filling this page). Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs
-5- 200300406 A7 B7 五、發明説明（$ (請先閱讀背面之注意事項再填寫本頁) 所產生的氣體以鹼性溶液捕捉，抑制發生ΝΟχ、，S Ox的一 種廢液處理方法。「濕式氧化」爲對需要處理的廢液供給 高溫-高壓水，更供給氧氣，將廢液予以氧化處理的一種廢 液處理方法。 但是’對含有丙烯酸的廢液之含酸性物質的廢液，一 般予先以鹼中和再供給處理裝置。 發明內容 本發係有鑑於上述問題點，提供丙烯酸的製造製程所 產生的廢水中有效的除去金屬之方法爲目的。 本發明者等爲解決上述問題點，進行各種檢討的結果 ’有關丙烯酸的製造製程所產生廢液至少一部份以濕式燃 燒、濕式氧化處理，其所發生的廢水中除去金屬的方法， 發現廢水中存在的金屬以多階段析出步驟，可有效率的除 去。 即，本發明如以下所述。 經濟部智慧財產局員工消費合作社印製 (1)由丙烷、丙烯及/或丙烯醛的氧相氧化而生成丙燒 酸，含蒸餾精製該丙烯酸的步驟之丙烯酸製造製程而生成 的廢液其至少一部份以濕式燃燒、濕式氧化處理所發生的 廢水中之金屬的除去方法， 含下步驟（a)〜（b)之丙烯酸製造廢水中除去金屬的方法 爲其特徵： (a) 上述廢水中除去固體物的步驟、 (b) 由上述（a)步驟所得的處理液除去碳酸離子及碳酸 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -6- 200300406 A7 B7 五、發明説明（$ 鹽的步驟、 (C)由上述（b)步驟所得的處理液除去金屬的步驟。 (請先閱讀背面之注意事項再填寫本頁) (2) 上述（C)步驟除去的金屬爲鉬及/或銅的（1)胃_ 酸製造廢水中除去金屬的方法。 (3) 與上述（a)步驟的同時或（a)步驟終了後，（b)步驟先 行除去銅後，上述（c)步驟除去的金屬爲鉬的（1)的丙烯酸製 造廢水中除去金屬的方法。 以下詳細明本發明。 本發明係由丙烷、丙烯及/或丙烯醛的氧相氧化而生成 丙烯酸之丙烯酸製造廢液其至少一部份以濕式燃燒、濕式 氧化處理所發生的廢水中之金屬的除去方法， 含下步驟（a)〜（b)丙烯酸製造廢水中除去金屬的方法爲 其特徵： U)上述廢水中除去固體物的步驟、 (b)由上述（a)步驟所得的處理液除去碳酸離子及碳酸 鹽的步驟、 由上述（b)步驟所得的處理液除去金屬的步驟。 經濟部智慧財產局員工消費合作社印製 有關本發明的丙烯酸製造廢水係由丙烷、丙烯及/或丙 烯醛的氧相氧化而生成丙烯酸，含蒸餾精製該丙烯酸的步 驟之丙烯酸製造製程而生成的廢液其至少一部份以濕式燃 燒、濕式氧化處理所發生的廢水。 丙烯酸的製造製程所產生的廢液，由於含醋酸或醛類 等的種種有機物質，此等有機物質採用以濕式燃燒或濕式 氧化變換爲無害的碳酸氣、水等的方法除去。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 200300406 A7 B7 五、發明説明（\ 「濕式燃燒」係廢液以燃燒處理的同時，由燃燒所產 生的氣體以鹼性溶液捕捉，抑制發生ΝΟχ、，S0X的一種廢 液處理方法。使用荷性鈉作爲鹼水溶液時，廢水中亦有荷 性鈉存在，再燃燒時大量碳酸氣以碳酸鈉的形態存在。 「濕式氧化」爲對需要處理的廢液供給高溫-高壓水， 更供給氧氣，將廢液予以氧化處理的一種廢液處理方法。 含酸性物質的廢液以濕式氧化處理時，爲防止裝置的腐蝕 一般以使用荷性鈉等作爲中和用，上時與濕式燃燒的情形 一樣，廢水中大量的碳酸氣以碳酸鈉等的形態溶解。 如上述丙烯酸的製造，催化劑的一部份爲氧化鉬、精 製時的助劑多數使用銅化合物，丙烯酸的製造製程所生成 的廢液中，含上述的金屬。該廢液以濕式燃燒、濕式氧化 處理所發生的廢水，當然含鉬、銅的金屬，與通常除去水 中的金屬比較，由此廢水中除去金屬較爲困難。此係濕式 燃燒、濕式氧化廢水中存在大量的碳酸離子及碳鹽的緣故 〇 廢液的濕式燃燒、濕式氧化處理依通常的方法進行。 由濕式燃燒、濕式氧化處理所得的廢水，無特別的限 制，通常持有下列組成。 廢水中金屬的一種爲銅，通常其含量爲40〜500重量 ppm，溶劑分爲1〇〜80重量ppm，固體成分的主體爲銅鹽 及銅的氧化物。 廢水中金屬的一種爲鉬，通常全數溶解，其濃度爲3〜 5 0 重量ppm 〇 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) 、1' 經濟部智慧財產局員工消費合作社印製-5- 200300406 A7 B7 V. Description of the invention ($ (please read the precautions on the back before filling this page) The gas generated is captured by alkaline solution to suppress the occurrence of NOx, SOx. "Wet oxidation" is a waste liquid treatment method that supplies high temperature-high pressure water to waste liquid that needs to be treated, and also supplies oxygen to oxidize the waste liquid. But 'for acid waste liquid containing acrylic acid, In general, alkali treatment is first supplied to the treatment device. SUMMARY OF THE INVENTION In view of the problems described above, the present invention aims to provide a method for effectively removing metals from wastewater generated by an acrylic acid manufacturing process. The present inventors and others have solved the above problems. The results of various reviews were conducted. 'At least a part of the waste liquid produced in the manufacturing process of acrylic acid is treated by wet combustion and wet oxidation. The method of removing metals from the waste water that has occurred has been found to The step precipitation step can be efficiently removed. That is, the present invention is as follows. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (1) by Oxygen phase oxidation of propane, propylene and / or acrolein to generate propionic acid. At least a part of the waste liquid generated by the acrylic acid manufacturing process including the step of distilling and refining the acrylic acid occurs by wet combustion and wet oxidation treatment. The method for removing metals from wastewater includes the following steps (a) to (b): a method for removing metals from acrylic acid manufacturing wastewater: (a) a step for removing solids from the wastewater, (b) from the above ( a) The treatment solution obtained in the step removes carbonic acid ions and carbonated paper. The size of the paper is applicable to the Chinese National Standard (CNS) A4 (210X297 mm)-6-200300406 A7 B7 5. Description of the invention ($ Salt step, (C) from the above (B) The step of removing metal from the treatment liquid obtained in step (Please read the precautions on the back before filling this page) (2) The metal removed in step (C) above is molybdenum and / or copper (1) Stomach_acid Method for removing metals in manufacturing wastewater. (3) Simultaneously with step (a) above or after step (a) ends, step (b) removes copper first, and the metal removed in step (c) is molybdenum (1) Removal of metals from acrylic acid manufacturing wastewater The present invention is described in detail below. The present invention is an acrylic acid manufacturing waste liquid that generates acrylic acid by the oxygen phase oxidation of propane, propylene, and / or acrolein. At least a part of the wastewater is produced by wet combustion and wet oxidation treatment. The method for removing metals in metal includes the following steps (a) to (b) The method for removing metals from acrylic acid wastewater: U) the step of removing solids from the wastewater, (b) obtained from the step (a) The step of removing carbonate ions and carbonates from the treatment liquid, and the step of removing metals from the treatment liquid obtained in the step (b) above. Printing by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The acrylic acid manufacturing wastewater related to the present invention is made of propane, propylene and At least a part of the waste liquid generated from the acrylic acid manufacturing process including the step of distilling and refining the acrylic acid is treated with wet combustion and wet oxidation treatment to generate acrylic acid. The waste liquid produced in the manufacturing process of acrylic acid contains various organic substances such as acetic acid and aldehydes, and these organic substances are removed by means of wet combustion or wet oxidation to be converted into harmless carbon dioxide gas and water. This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) 200300406 A7 B7 V. Description of the invention (\ "Wet Combustion" refers to the waste liquid used for combustion treatment, and the gas produced by the combustion is used as an alkaline solution. A waste liquid treatment method that captures and suppresses NOx, S0X. When charged sodium is used as an alkaline aqueous solution, there is also charged sodium in the wastewater, and a large amount of carbon dioxide gas is present in the form of sodium carbonate when reburning. "Wet oxidation "It is a waste liquid treatment method for supplying high temperature-high pressure water to the waste liquid to be treated, and also supplying oxygen, and oxidizing the waste liquid. When the waste liquid containing acidic substances is treated by wet oxidation, it is generally used to prevent corrosion of the device. It uses neutralized sodium as neutralizing agent. In the same way as in the case of wet combustion, a large amount of carbon dioxide gas in the wastewater is dissolved in the form of sodium carbonate, etc. As in the production of acrylic acid mentioned above, part of the catalyst is molybdenum oxide, Most of the auxiliaries used in the purification process are copper compounds, and the waste liquid produced by the acrylic acid manufacturing process contains the above metals. The waste liquid is wet-burned and wet-oxidized Of course, the wastewater that is generated, of course, contains metals containing molybdenum and copper. Compared with metals that are usually removed from water, it is more difficult to remove metals from the wastewater. This system contains a large amount of carbonate ions and carbon in wet combustion and wet oxidation The sake of salt 〇 Wet combustion and wet oxidation treatment of waste liquid are carried out according to a usual method. Wastewater obtained by wet combustion and wet oxidation treatment is not particularly limited and generally has the following composition. One of the metals in wastewater It is copper, usually its content is 40 to 500 weight ppm, the solvent is divided into 10 to 80 weight ppm, and the main component of the solid component is copper salt and copper oxide. One of the metals in the wastewater is molybdenum, which is usually fully dissolved and its concentration 3 ~ 50 0 ppm by weight 〇 This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page), 1 'Printed by the Intellectual Property Bureau Employees Consumer Cooperatives system
-8- 200300406 A7 B7 五、發明説明（$ 碳微粒子低於 1重量 ppm，不正常時會增加數重量 ppm 〇 (請先閲讀背面之注意事項再填寫本頁) 鈉爲〇.2〜8重量％，主要以碳酸鈉及荷性鈉存在。 處理後的廢水其pH爲8〜10.2，濕式燃燒、濕式氧化 處理的廢水排出時的溫度一般在80°C以上。 本發明濕式燃燒、濕式氧化處理所產生的廢水依以下 的步驟處理，有效的除去廢水中之金屬的方法。 有關本發明上述（a)步驟廢水中除去固體物的步驟，係 將以固體成分存在的銅凝結-沈澱，容易固液分離，得到處 理液（以下除去固體成分的處理液以「處理液1」稱之）的步 驟。例如，廢水添加凝結劑使其發生固體成分，該固體成 分使用沈澱槽、使用膜分離等除去，可得到處理液1。 廢水中存在的固體成分，以銅爲主要的來源，具體的 如 Cu20、Cu2 (C03) (OH)2 、CuO、Cu 等。 經濟部智慧財產局員工消費合作社印製 有關（a)步驟發生固體成分的方法，爲使金屬濃度更低 ，一般倂用析出劑，不倂用析出劑而僅用凝結劑的理由， 係析出劑將銅析出外，亦會將其他的固體形態（例如碳酸銅） 存在的銅分溶解，結果溶液中銅的濃度幾乎不下降。爲使 銅濃度下降，對已溶解的銅濃度不得不加入大量過剩的析 出劑，（a)步驟使用析出劑多數不能得到期待的效果，在經 濟上不利。 使用於（a)步驟的凝結劑，以陽離子系高分子凝結劑爲 理想。具體例歹丨J舉如 DIACLEAR-MK、MK-5000(日本 DIANITOREX(株）製），ARONFLOCK C-303(曰本東亞合成（ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -9- 200300406 A7 B7 五、發明説明（$ 株）製）、NALCO 1 450、1460(曰本 NALCΟ JAPAN(株）製） 等。廢液添加凝結劑的添加量以〇 〇 〇 1〜2重量％爲理想。 步驟所使用的沈澱槽係爲分離添加凝結劑所生成的固 體成分的槽。所發生的固體通常於數分鐘沈降。（a)步驟不 必要將固體成分與液體完全分離，除去大部份的固體即可 〇 發明所使用的沈澱槽，可舉例如底部爲錐形（圓錐型）的 圓筒型容器或容器內設置複數的傾斜板圓筒型或多柱型容 此操作可減少1 〇〜3 0重量p p m銅離子濃度。鉬的濃 度無變化。 不使用沈澱槽以膜分離時，不必要捕捉微粒子亦可。 溶解的銅離子爲1 〇重量ΡΡ Π1以上所以效果低。有關本發明 所使用的膜分離的手段，有中空系膜的濾別法等，具體的 如日本KURARE製Kurare SF過濾器或日本旭化成工業（株 )製的 Microzer MF 等。 如上述得到處理液1。又（a)步驟，除去固體成分可僅 操作一次，以進行複數次爲理想。如此則可更降低銅濃度 〇 步驟除去固體成分的步驟進行二次以上時，所得的處 理液1，添加析出劑，理想爲倂用凝結劑添加析出固體成分 ，該固體成分使用上述沈澱槽、膜分離等手段等（以下以「 濾別」稱之）除去。此處所使用的析出劑爲硫化合物，例如 二甲基氨基甲酸酯、三巯基三嗪、硫酸鈉、或聚胺系出劑 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） (請先閱讀背面之注意事項再填寫本頁) •裝·-8- 200300406 A7 B7 V. Description of the invention ($ Carbon fine particles are less than 1 ppm by weight, which will increase by several ppm when abnormal. 〇 (Please read the precautions on the back before filling this page) Sodium is 0.2 ~ 8 weight %, Mainly in the presence of sodium carbonate and charged sodium. The pH of the treated wastewater is 8 to 10.2, and the temperature of the wastewater from wet combustion and wet oxidation treatment is generally above 80 ° C. The wet combustion of the invention, The wastewater generated by the wet oxidation treatment is processed according to the following steps to effectively remove metals in the wastewater. The step of removing solids from the wastewater of the step (a) of the present invention is to condense copper existing as a solid component- Precipitation and easy solid-liquid separation to obtain a treatment liquid (hereinafter referred to as "treatment liquid 1" for removal of solid components). For example, a coagulant is added to the wastewater to produce a solid component. Removal by membrane separation, etc., can obtain the treatment liquid 1. The solid components present in the wastewater are mainly copper, such as Cu20, Cu2 (C03) (OH) 2, CuO, Cu, etc. Ministry of Economic Affairs The method for printing solid components in step (a) produced by the Bureau ’s Consumer Cooperative is to use a precipitating agent instead of a precipitating agent in order to lower the metal concentration. , Will also dissolve the copper in other solid forms (such as copper carbonate), and the copper concentration in the solution will hardly decrease. In order to reduce the copper concentration, a large amount of excess precipitation agent must be added to the dissolved copper concentration, Most of the precipitation agents used in step (a) cannot obtain the desired effect and are not economically advantageous. The coagulant used in step (a) is preferably a cationic polymer coagulant. Specific examples include JACL such as DIACLEAR-MK, MK-5000 (manufactured by Japan's DIANITOREX Co., Ltd.), ARONFLOCK C-303 (Japanese paper of East Asia Synthetic (applicable to Chinese National Standard (CNS) A4 size (210X297 mm) for this paper size) -9-200300406 A7 B7 V. Description of the invention ( (Manufactured by Co., Ltd.), NALCO 1 450, 1460 (manufactured by Narco Japan Co., Ltd.), etc. The amount of coagulant added to the waste liquid is preferably 0.001 to 2% by weight. The precipitation tank used in the step It is a tank for separating solid components generated by adding a coagulant. The solids usually settle within a few minutes. (A) It is not necessary to completely separate the solid components from the liquid, and most of the solids can be removed. Used in the invention The sedimentation tank can be, for example, a cylindrical container with a conical (conical) bottom or a plurality of inclined plate cylindrical or multi-column types. This operation can reduce the concentration of copper ion by 10 to 30 ppm by weight. There is no change in the concentration of molybdenum. It is not necessary to capture fine particles when using a precipitation tank for membrane separation. Dissolved copper ions are at least 10 wt. PP Π1, so the effect is low. As a means of membrane separation used in the present invention, there is a filtration method of a hollow membrane, and specific examples include a Kurare SF filter manufactured by Kurare, Japan, or a Microzer MF manufactured by Asahi Kasei Corporation. The treatment liquid 1 was obtained as described above. In the step (a), the solid content can be removed only once, and a plurality of times is preferable. In this way, the copper concentration can be further reduced. When the step of removing the solid content is performed twice or more, a precipitation agent is added to the treatment liquid 1 obtained, and it is desirable to add a precipitated solid content using a coagulant. Separation and other means (hereinafter referred to as "filtration") are removed. The precipitating agent used here is a sulfur compound, such as dimethyl carbamate, trimercaptotriazine, sodium sulfate, or polyamine-based effluent. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 × 297 mm). (Please read the notes on the back before filling this page)
、1T 經濟部智慧財產局員工消費合作社印製 -10- 200300406 A7 B7 五、發明説明（} ，例如日本NALCO JAP AN(株）販賣的NALMET等，添加量 (請先閲讀背面之注意事項再填寫本頁) 爲對銅（金屬）的重量之5〜3 0倍爲理想。凝結劑可使用與 (a)步驟的第一次發生固體成分所使用的相同品，添加量爲 處理對象物的重量的〇.〇1〜2重量％爲理想。 又，金屬分離廣泛使用的氫氧化鈉或氫氧化鉀等的強 鹼基而析出金屬氫氧化物方法，其次的步驟脫碳酸處理時 的酸的使用量會增加，不太理想。 本發明的（b)步驟，係由上述處理液1除去酸離子及碳 酸鹽的步驟。 由處理液1除去酸離子及碳酸鹽，係爲此後的（c)步驟 有效率的析出溶解金屬。 除去酸離子及碳酸鹽（以下以「脫鹽酸」稱之）的方法， 係於處理液1添加硫酸、鹽酸等的酸，碳酸基部份氣化爲 二氧化碳放出的方法。又，爲提高二氧化碳放出的速度， 可將處理液加溫（以下由脫碳酸所得的處理液以「處理液2 」稱之）。 經濟部智慧財產局員工消費合作社印製 碳酸離子及碳酸鹽未除去而進行（c)步驟時（爲除去金屬 而添加析出劑時），發生以下的問題。 (1) 添加析出劑時pH發生化發生碳酸的微泡，將析出 的固體浮遊，有難於沈降-分離傾向。 (2) 由於處理液1中所含的碳酸鈉對pH緩衝作用，不 易微調pH 。 (3) 由於碳酸的存在，（c)步驟必要添加大量的析出劑。 又’（a)步驟不進行除去固體成分，一開始就進行脫碳 本紙張尺度適财關家縣（CNS ) A4規格（21GX297公釐) ~ 一~" -11 - 200300406 A7 B7 五、發明説明（$ 酸時，廢水中既已固體成分存在的銅鹽，由添加酸（pH下降 )而溶解。又，此時必需的酸量（僅固體成溶解所消費部份） 亦增多。爲再度沈降被溶解的銅’次步驟使用的析出劑的 用量必當然增加不理想。 脫碳酸了後，確認pH爲一定値（4.0)。 有關本發明（c)步驟係由上述處理液2除去金屬的步驟 ，該步驟除去的金屬，以鉬及 /或銅爲主。上述（a)步驟 除去固體成分的步驟分二次以上進行時，（c)步驟所除去的 金屬爲組。 由處理液2，除去鉬及銅的金屬的方法，係爲析出處理 液2中溶存的銅而添加析出劑，銅成分沈降成固體成分除 去後，爲鉬的析出而添加析出劑，理想爲倂用凝結劑，銅 成分以沈降成固體成分除去的方法。 (c)步驟所使用爲析出銅的析出劑可列舉如氫氧化鈉、 氫氧化鉀等，處理液中的銅成爲氫氧化銅析出。又，爲析 出鉬的析出劑爲二價或三價的鐵鹽，可列舉如氯化鐵（III) 、硫酸鐵（Π)、NALC0813 1(日本 NALCO JAPAN(株）製）等 ，凝結劑以陰離子的高分子凝結劑爲理想。具體的可舉例 如 SOILHARD(曰本 DIANITOREX(株）製）、DIACLEAR MA( 曰本 DIANITO REX (株）製），ARONFLOCK A-104，A-101( 曰本東亞合成（株）製），NALCO9601(日本DIANITOREX(株） 製）等。 處理液2所添加的析出劑添加量，銅的析出劑爲銅的 重量的5〜3 0倍量爲理想，鉬的析出劑爲鉬的重量的3〜 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) 裝· 訂 經濟部智慧財產局員工消費合作社印製 -12- 200300406 A7 B7 五、發明説明（$ 3 〇倍量爲理想，凝結劑的使用量爲處理對象物的0.0 1〜2 重量％爲理想。 沈降的固體成分以濾別等除去。 (a)步驟除去固體成分的步驟分二次以上進行時，（c)步 驟僅進行除去鉬。 又，上述（a)步驟、（c)步驟所生成的固體成分，由於含 有大量的水份，此等以壓濾器或離心分離（脫水）機等降低水 分含量至5 0 %程度，除去固體成分的液，循環至爲除去金 屬的步驟（a)〜（c)等的任一步驟爲理想。 如上述，除去金屬的廢水，充分符合環境基準者，原 樣排放無問題。又，可再利用於丙烯酸的製造製程。 f%先閱讀背面之注意事項再填寫本頁) •裝· 訂 實施方式 以下，以圖來說明本發明的一種實施形態，本發明不 限定於此形態。 圖1所示爲本發明的一種實施的形態系統圖。 經濟部智慧財產局員工消費合作社印製 首先，已濕式燃燒裝置處理的廢水中添加凝結劑1，於 沈澱槽1除去固體成分，得到處理液l((a)步驟）。因除去的 固體成分亦含液體，以離心機或壓濾器等分離液體，爲除 去該液體中的金屬，使其再循序漸進爲理想。 其次，處理液1中添加析出劑2、凝結劑2，析出的固 體成分於沈澱槽2除去。更加入酸，進行脫碳酸’得到處 理液2((b)步驟）。所得的處理液2中添加析出劑3、凝結劑 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -13- 200300406 A7 B7 五、發明説明（）0 (請先閲讀背面之注意事項再填寫本頁) 3，析出的固體成分於沈澱槽3除去，成爲最終處理液。 實施例 以下以實施例及比較例更具體的說明本發明，本發明 不超越其要旨的限度本發明不限定於實施例。 有關實施例所使用的藥劑如以下所述。 藥劑①：NALCO 1460(曰本 NALCO JAPAN(株）製） 藥劑 0 : NALMATE(曰本 NALCO JAPAN(株）製） 藥劑③·· NALCO 8 13 1(曰本 NALCO JAPAN(株）製） 藥劑④：NALCO 9601(曰本 NALCO JAPAN(株）製） 實施例1 <廢液組成> 由丙烯酸製造製程發生的廢液以濕式燃燒裝置進行濕 式燃燒處理時，發生下述組成的茶褐色廢水（如泥水）。 銅：2〇〇重量ppm(含固體成分） 鉬：1 0重量 p p m 經濟部智慧財產局員工消費合作社印製 固體成分總量：6 0 0重量 p p m pH : 9.4 <操作1-1>添加凝結劑（（a)步驟的除去固體成分） 對全量廢水添加4重量ppm的凝結劑（藥劑①），攪拌 3分鐘後，靜置3分鐘。固體分全數（目視）凝結沈降濾別後 ，得到處理液1。 處理液1僅帶極微的透明藍色，處理液1的金屬濃度 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 14- 200300406 A7 B7 五、發明説明（ 爲銅5重量 ppm，鉬10重量 ppm。 <操作1-2>添加析出劑+凝結劑（除去銅） (請先閱讀背面之注意事項再填寫本頁) 對上述〈操作1·1>所得的處理液1，添加30重量ppm 的析出劑（藥劑②）後攪拌5分鐘後，添加4重量ppm的凝 結劑（藥劑①），攪拌3分鐘後，靜置3分鐘。 固體分全數（目視）凝結沈降濾別。所得的處理液爲無色 透明，金屬濃度爲銅0.1重量ppm，鉬10重量 ppm。 <操作1-3 >調整pH ((b)步驟的脫碳酸） 對上述<操作1-2>所得的處理液，邊攪拌邊添加5000 重量 ppm的硫酸，調整pH爲4，得到處理液2。 <操作1_4>添加析出劑+凝結劑（（c)步驟的除去金屬（鉬）） 對上述<操作1-3 >所得的處理液2，添加50重量ppm 的析出劑（藥劑③）後攪拌5分鐘後，添加4重量ppm的凝 結劑（藥劑④），攪拌3分鐘後，靜置3分鐘。 固體分全數（目視）凝結沈降瀘別後，得到最終處理液， 最終處理液爲無色透明，最處理液中的金屬濃度爲銅<〇. 1 重量 ppm，鉬0.5重量 ppm。詳如表1。 經濟部智慧財產局員工消費合作社印製 實施例2 <操作2-l>((a)步驟的除去固體成分） 使用實施例同樣的廢水，僅攪拌1分鐘放置1小時， 不使用凝結劑沈降固體成分，濾別得到處理液1。處理液1 由於微粒子浮游’稍爲不透明，處理液1的金屬濃度爲銅 30重量 ppm，銷10重量 ppm。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -15- 200300406 A7 ___ B7 五、發明説明（）2 <操作2-3>調整pH ((b)步驟的脫碳酸） (請先閱讀背面之注意事項再填寫本頁) 對上述 <操作2_2>所得的處理液，邊攪拌邊添加5500 重量 ppm的硫酸，調整pH爲4，得到處理液2。 <操作2-4’>((c)步驟的除去（銅）） 處理液2添加氫氧化鈉水溶液（氫氧化鈉8 0 0重量p p m ) 後攪拌3分鐘後，靜置20分鐘濾別。上澄淸液的pH爲1 〇 ，金屬濃度爲銅2.0 ppm，|目10重量 ppm。 <操作2-4>((c)步驟的除去金屬（鉬）） 對上述<操作2-4’>所得的澄淸液，進行與實施例1的< 操作〗_4> ’得到最終處理液。最終處理液爲無色透明，金 屬濃度爲銅1 ppm，鉬1重量 ppm。又，最終處理液的硫 酸濃度爲300重量 ppm。詳如表1。 實施例3 <操作3-2>(除去（銅）） 經濟部智慧財產局員工消費合作社印製 不進行實施例1的 <操作1 -1 >，除對廢水的藥劑0的量 改爲1 500重量ppm以外，進行實施例1同樣的 <操作 ，得到處理液1。處理液爲無色透明，金屬濃度爲銅2重量 ppm，鉬 10 重量 ppm。 <操作3-3>調整pH ((b)步驟的脫碳酸） 對上述<操作3 _2>所得的處理液1，邊攪拌邊添加5 00 0 重量 ppm的硫酸，調整pH爲4，得到處理液2。 <操作3_4>((c)步驟的除去金屬（鉬）） 對上述<操作3-3 >所得的處理液2，進行與實施例的< 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -16- 200300406 A7 B7 五、發明説明（）3 操作1 _4>，得到最終處理液。最終處理液爲無色透明，金 屬濃度爲銅〇·3 ppm，鉬0.9重量 ppm。詳如表1所示。 (請先閲讀背面之注意事項再填寫本頁) 比較例1 <操作4-4>((c)步驟的除去金屬（鉬）） 有關實施例3，不進行操作3-3(脫碳酸），對上述3-2 所得的處理液1，除藥劑③的使用量改爲 1〇〇〇 ppm外，進 行與實施例的 <操作1 -4>，得到最終處理液。最終處理液爲 無色透明，金屬濃度爲銅1.1 ppm，鉬2.0重量ppm。詳如 表1所示。 比較例2 <操作5-3 >調整pH ((b)步驟的脫碳酸） 不進行實施例1所進行的操作1-1除去固體成分及操 作1-2(除去銅），對廢水邊攪拌邊添加83〇〇重量ppm的硫 酸，調整pH爲4，得到處理液2。 <操作5-4’>((c)步驟的除去（銅）） 經濟部智慧財產局員工消費合作社印製 處理液2添加氫氧化鈉水溶液（氫氧化鈉23 00重量 p p m)後攪拌3分鐘後，靜置20分鐘濾別。上澄淸液的pΗ 爲10’金屬濃度爲銅3.3 ppm，鉬10重量 ppm。 <操作5_4> ((c)步驟的除去金屬（鉬）） 對上述<操作5-4，>所得的澄淸液，除藥劑③的使用量 改爲1 000 ppm外，進行與實施例1的 <操作1_4>，得到最 終處理液。最終處理液爲無色透明，金屬濃度爲銅2.〇 ρρηι 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -17- 200300406 A7 B7 五、發明説明（）4 ’鉬1.7重量ppm。詳如表1所示。 (請先閲讀背面之注意事項再填寫本頁) 比較例3 <操作6-l>((a)步驟的除去固體成分） 使用實施例同樣的廢水，與實施例1同樣得到處理液1 。處理液1僅帶極微的透明藍色，處理液1的金屬濃度爲 銅15重量 ppm，鉬10重量 ppm。 <操作6-2>(除去（銅）） 對上述 <操作6_1>所得的處理液1，添加30重量 ppm 的析出劑（藥劑②）後攪拌5分鐘後，添加4重量ppm的凝 結劑（藥劑①），攪拌3分鐘後，靜置3分鐘。 固體分全數（目視）凝結沈降濾別。所得的處理液爲無色 透明’金屬濃度爲銅0.1重量 ppm，自目10重量 ppm。 <操作6-4>((c)步驟的除去金屬（鉬）） 經濟部智慧財產局員工消費合作社印製 對上述 <操作6-3〉所得的澄淸液，除藥劑③的使用量改 爲 1〇〇〇 ppm外，進行與實施例1的 <操作1-4>，得到最終 處理液。最終處理液爲無色透明，金屬濃度爲銅0.1 ppm， 鉬2.0重量 p p m。詳如表1所示。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -18- 200300406 A7 B7 五、發明説明（）|5 經濟部智慧財產局員工消費合作社印製 除去(鉬)金屬 Ε E d §： E品 § 寸 〇_ • · · · Q. Θ 0 ^ 敬勸：V 潞潞骠 Ε Ε §= Ε & Ε 二 §: S § 10寸民 CO ·* ·· α： ·· CD © @ τ- 觀1 S贏·· 握五嫌歡骠 Ε α. σ> ο ε & Ε ™ g 〇： Ε ° ^ §： © @ d 雛髁骠 Ε Q. Ε ^ α. Q. C ΠΠ I it S §： © @ ^ S S ·_ 鄹攤骠 1 1 °· E ^ Q. ^ E °· E ·· & 8 a i § s - 1 0〇···*〇； ••❺ @ CM 觀観s ·· 磨鄹鄹骠 E g ε cm α. ^ E ttn O Q. § ^ E '""< 寸 〇 • · · · Θ Θ ^ 攤激骠 除去(銅)金屬 1 | Q. § 蓼 〇〇 Ε Q. 噚 〇 ^ 2 CM* 祕》 " 礙Q· 疆 I I E E ! §: - § 翠 CNJ E Q. rS! 。 ^ CO ^ 2 CO 祕" ·· 藏〇_ 疆 ! 脫碳酸 E Q. 〇 UO 8i 〇. E 〇. 〇 1〇 k 1 Ε Q- 〇 1 m 1 ig ξ. I E g 〇 S m l 1 除去銅 Ε g Ιΐ! CO寸g ® Θ d s蘅·· 鄹歡骠 1 1 1 2 α. c ·· 1 '^寸 Ε • · ο. ®㊀CM 觀g ·_ 厳歡骠 1 1 ^ Q. ρ ·· 1 af r 寸 Ε .. ♦· Cl ❾㊀C\J S g _· 纖赚骠 1 ε ο. ο ! ι舉 i "1 ® θ d 藏s _· 纖灘骠 除去固體成分 Ε Q. Ο τ— Ε ππ 8= f θ ί 蘅 激 骠 ε Q. Ο τ— 題 Ε ο. 1 區 盤 Ε S 區 Η n s 驅 Μ 鄯 1 Ε α. ο Ε ππ §= f 7 g= θ ί S Ε 骠 i 辑 IK CM 習 IK ¢0 揭 Ιϋ ί 鎰 i5 CM i3 CO 鎰 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -19- 200300406 A7 ___ B7 五、發明説明（、6 商業上之利用領域 依本發明，丙烯酸的製造製程所產生廢液以濕式燃燒 、濕式氧化處理，其所發生的廢水中的金屬可有效的除去 〇 圖式簡單說明 圖1所示爲本發明的除去廢水中金屬的方法之實施的 形態系統圖。 主要元件對照表 1 濕式燃燒裝置 2 凝結劑1 3 沈澱槽1 4 析出劑2 5 凝結劑2 6 沈澱槽2 7 酸 8 脫碳酸 9 析出劑3 10 凝結劑3 11 沈澱槽3 12 離心機或壓濾機 13 固體成分 14 回製程再循序漸進 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) -裝· 經濟部智慧財產局員工消費合作社印製 -20- 200300406 A7 B7 五、發明説明（、Ί 15 排水 (請先閱讀背面之注意事項再填寫本頁) -裝· 訂 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） -21 -1. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-10-200300406 A7 B7 V. Description of the invention (), such as NALMET sold by Japan's NALCO JAP AN Co., Ltd., the amount added (please read the precautions on the back before filling (This page) Ideally, it is 5 to 30 times the weight of copper (metal). The coagulant can be the same as that used for the first occurrence of solid components in step (a), and the added amount is the weight of the object to be treated. 〇1〜2 重量 ％ is ideal. In addition, the metal is separated from strong bases such as sodium hydroxide and potassium hydroxide, which are widely used, and a metal hydroxide is precipitated. The second step is the use of an acid during decarbonation. The amount will increase, which is not ideal. Step (b) of the present invention is a step of removing acid ions and carbonates from the treatment liquid 1. The removal of acid ions and carbonates from the treatment liquid 1 is the subsequent step (c). Efficient precipitation of dissolved metals. A method of removing acid ions and carbonates (hereinafter referred to as "dehydrochloric acid") is a method in which acid such as sulfuric acid and hydrochloric acid is added to the treatment liquid 1, and the carbonate group is gasified to release carbon dioxide. .also In order to increase the rate of carbon dioxide emission, the treatment liquid can be heated (the treatment liquid obtained by decarbonation is hereinafter referred to as "treatment liquid 2"). Carbonate ions and carbonates printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs are not removed. However, when step (c) is performed (when a precipitation agent is added to remove metals), the following problems occur: (1) When the precipitation agent is added, the pH is changed to generate carbonic acid microbubbles, and the precipitated solids float, making it difficult to settle and separate. (2) Because of the buffering effect of sodium carbonate contained in the treatment solution 1, it is difficult to fine-tune the pH. (3) Due to the presence of carbonic acid, it is necessary to add a large amount of a precipitating agent in step (c). Carry out the removal of solid components, and decarbonize the paper at the beginning. The paper size is suitable for Guancai County (CNS) A4 size (21GX297 mm) ~ 1 ~ " -11-200300406 A7 B7. 5. Description of the invention ($ acid, waste water The copper salt that already exists in the solid component is dissolved by the addition of acid (pH decreases). At this time, the amount of acid (only the solid consumed to dissolve the part consumed) is also increased. The copper that is dissolved is re-settled for a second time. Steps to use Of course, the amount of the precipitating agent must be increased undesirably. After decarbonation, it is confirmed that the pH is constant (4.0). Regarding the step (c) of the present invention, the step of removing the metal from the treatment liquid 2 described above, the metal removed in this step is molybdenum And / or copper. When the step of (a) removing the solid content is performed twice or more, the metal removed in step (c) is a group. The method for removing the metal of molybdenum and copper from the treatment liquid 2 is A precipitation agent is added to precipitate the copper dissolved in the treatment liquid 2 and the copper component is precipitated to be a solid component and removed, and then a precipitation agent is added to precipitate molybdenum. A coagulant for concrete is preferably used, and the copper component is removed by sedimentation to a solid component. Examples of the precipitating agent used in the step (c) for precipitating copper include sodium hydroxide, potassium hydroxide, and the like, and copper in the treatment liquid is precipitated as copper hydroxide. In addition, the precipitation agent for depositing molybdenum is a divalent or trivalent iron salt, and examples thereof include iron (III) chloride, iron (II) sulfate, NALC0813 1 (manufactured by NALCO JAPAN Co., Ltd.), and the like. Anionic polymer coagulants are preferred. Specific examples include SOILHARD (manufactured by DIANITOREX Co., Ltd.), DIACLEAR MA (manufactured by Dianito Rex Co., Ltd.), ARONFLOCK A-104, A-101 (manufactured by Tohoku Toa Synthetic Co., Ltd.), NALCO9601 ( Made by Japan Dianitorex Co., Ltd.). The amount of the precipitation agent added to the treatment liquid 2 is preferably 5 to 30 times the weight of copper, and the precipitation agent of molybdenum is 3 to 3 times the weight of molybdenum. This paper applies Chinese national standards (CNS). A4 specifications (210X297 mm) (Please read the notes on the back before filling this page) Binding and printing Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-12- 200300406 A7 B7 V. Description of the invention ($ 300. Ideally, the amount of coagulant used is preferably 0.0 1 to 2% by weight of the object to be treated. Settled solids are removed by filtration, etc. (a) When the step of removing solids is performed in two or more steps, (c) Only the removal of molybdenum is performed in the step. In addition, since the solid components generated in the above steps (a) and (c) contain a large amount of water, the moisture content is reduced to 50 by a filter press or a centrifugal separation (dehydration) machine. It is desirable that the solid content-removing liquid is recycled to any one of steps (a) to (c) for removing metals. As described above, if the metal-removing wastewater fully meets the environmental standards, there is no problem in its discharge as it is. Again It is used in the manufacturing process of acrylic acid. F% read the precautions on the reverse side before filling in this page) • Binding and binding Embodiments The following is an illustration of one embodiment of the present invention, but the present invention is not limited to this embodiment. FIG. 1 shows a morphological system diagram of an embodiment of the present invention. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs First, the coagulant 1 is added to the wastewater treated by the wet combustion device, and the solid content is removed in the sedimentation tank 1 to obtain a treatment liquid 1 (step (a)). Since the solids to be removed also contain liquid, the liquid is separated by a centrifuge or a filter, etc. It is ideal to remove the metal from the liquid and make it progressive. Next, a precipitating agent 2 and a coagulant 2 are added to the treatment liquid 1, and the precipitated solid components are removed in the precipitating tank 2. Further, an acid was added, and decarbonation was performed to obtain a treatment liquid 2 (step (b)). Adding precipitation agent 3 and coagulant to the obtained treatment liquid 2. The paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) -13- 200300406 A7 B7 V. Description of the invention () 0 (Please read the note on the back first (Please fill in this page again for details) 3. The precipitated solids are removed in the precipitation tank 3 and become the final treatment solution. Examples The present invention will be described more specifically with reference to examples and comparative examples below. The present invention does not exceed the gist of the present invention, and the present invention is not limited to the examples. The drugs used in the examples are as follows. Pharmacy ①: NALCO 1460 (manufactured by Nalco Japan Co., Ltd.) Pharmacy 0: NALMATE (manufactured by Nalco Japan Co., Ltd.) Pharmacy ③ · NALCO 8 13 1 (manufactured by Nalco Japan Co., Ltd.) Pharmacy ④: NALCO 9601 (manufactured by NALCO JAPAN Co., Ltd.) Example 1 < Waste liquid composition > When the waste liquid generated from the acrylic acid manufacturing process is subjected to wet combustion treatment in a wet combustion device, a tea brown waste water having the following composition ( (Such as muddy water). Copper: 2000 ppm by weight (including solid content) Molybdenum: 10 ppm by weight Total printed solid content by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs: 60 ppm by weight pH: 9.4 < Operation 1-1 > Add condensation Agent (removal of solid content in step (a)) A coagulant (agent ①) was added at 4 weight ppm to the entire amount of wastewater, and after stirring for 3 minutes, it was allowed to stand for 3 minutes. All solids were visually condensed, settled, and filtered to obtain Treatment Liquid 1. The treatment liquid 1 has only a slight transparent blue color. The metal concentration of the treatment liquid 1 is based on the Chinese National Standard (CNS) A4 specification (210X297 mm). 14- 200300406 A7 B7 5. Description of the invention (for copper 5 ppm by weight, 10 ppm by weight of molybdenum. ≪ Operation 1-2 > Add precipitation agent + coagulant (remove copper) (Please read the precautions on the back before filling this page) Add the treatment liquid 1 obtained in the above <Operation 1.1 ·> 30 weight ppm of the precipitant (agent ②) was stirred for 5 minutes, and then 4 weight ppm of the coagulant (agent ①) was added, and after stirring for 3 minutes, it was allowed to stand for 3 minutes. The entire solid content (visual) was coagulated and settled and filtered. The obtained The treatment solution is colorless and transparent, with a metal concentration of 0.1 wtppm of copper and 10 wtppm of molybdenum. ≪ Operation 1-3 > pH adjustment (decarbonation of step (b)) For the above < Operation 1-2 > Add 5,000 ppm by weight of sulfuric acid while stirring the treatment liquid and adjust the pH to 4 to obtain treatment liquid 2. < operation 1_4 > add precipitation + coagulant (metal removal (molybdenum) in step (c)) to the above < Operation 1-3 > The obtained treatment liquid 2 was added at 50 ppm by weight After precipitating agent (agent ③) was stirred for 5 minutes, 4 weight ppm of coagulant (agent ④) was added, and after stirring for 3 minutes, it was allowed to stand for 3 minutes. All solids (visual) were condensed and settled, and the final treatment solution was obtained. The final treatment liquid is colorless and transparent, and the metal concentration in the most treatment liquid is copper < 0.1 weight ppm and molybdenum 0.5 weight ppm. For details, please refer to Table 1. Example 2 printed by the Intellectual Property Bureau employee consumer cooperative of the Ministry of Economic Affairs < Operation 2-l> (Removal of solid content in step (a)) Using the same wastewater as in the example, only stirring for 1 minute and leaving it for 1 hour, without using a coagulant to settle the solid content, the filtration solution 1 was obtained. The treatment fluid 1 was fine particles The 'floating' is slightly opaque. The metal concentration of the treatment liquid 1 is 30 ppm by weight of copper and 10 ppm by weight. The paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -15- 200300406 A7 ___ B7 V. Invention Explanation () 2 < Operation 2-3 > Adjusting pH (Decarbonation of step (b)) (Please read the precautions on the back before filling in this page) For the treatment liquid obtained in < Operation 2_2 >, while stirring Add 5500 weight The amount of ppm of sulfuric acid was adjusted to pH 4 to obtain a treatment solution 2. < Operation 2-4 '> (Removal of (c) step (copper)) The treatment solution 2 was added with an aqueous sodium hydroxide solution (sodium hydroxide 8 0 0 After stirring for 3 minutes, the mixture was left to stand for 20 minutes, and filtered. The pH of the upper solution was 10, the metal concentration was 2.0 ppm copper, and 10 ppm by weight. < operation 2-4 > (removal of metal (molybdenum) in step (c)) With respect to the above-mentioned < operation 2-4 '>, the clarified solution obtained was subjected to < operation > _4 > The final treatment solution. The final treatment solution was colorless and transparent, with a metal concentration of 1 ppm copper and 1 ppm by weight of molybdenum. The sulfuric acid concentration of the final treatment solution was 300 ppm by weight. See Table 1 for details. Example 3 < Operation 3-2 > (removal (copper)) The Intellectual Property Bureau, Ministry of Economic Affairs, Employee Consumer Cooperative Co., Ltd. does not print the < operation 1 -1 > Except for 1 500 weight ppm, the same < operation as in Example 1 was performed to obtain a treatment liquid 1. The treatment liquid is colorless and transparent, and the metal concentration is 2 ppm by weight of copper and 10 ppm by weight of molybdenum. < Operation 3-3 > Adjusting pH (decarbonation of step (b)) With respect to the treatment liquid 1 obtained in < Operation 3_2 > described above, 50000 ppm by weight of sulfuric acid was added while stirring, and the pH was adjusted to 4 to obtain Treatment liquid 2. < Operation 3_4 > (Removal of metal (molybdenum) in step (c)) For the treatment liquid 2 obtained in < Operation 3-3 >, the same as in the examples are applied to this paper standard. Chinese paper standard (CNS) A4 specification (210X297 mm) -16- 200300406 A7 B7 V. Description of the invention () 3 Operation 1 _4 > to obtain the final processing solution. The final treatment solution was colorless and transparent, with a metal concentration of 0.3 ppm of copper and 0.9 weight ppm of molybdenum. Details are shown in Table 1. (Please read the precautions on the back before filling in this page) Comparative Example 1 < Operation 4-4 > (Removal of metal (molybdenum) in step (c)) Regarding Example 3, operation 3-3 is not performed (decarbonation) With respect to the treatment liquid 1 obtained in the above 3-2, except that the usage amount of the agent ③ was changed to 1000 ppm, the < operation 1-4 > with the example was performed to obtain a final treatment liquid. The final treatment liquid was colorless and transparent, with a metal concentration of 1.1 ppm for copper and 2.0 ppm by weight for molybdenum. The details are shown in Table 1. Comparative Example 2 < operation 5-3 > pH adjustment (decarbonation of step (b)) The operation 1-1 performed in Example 1 was not performed to remove solid components and the operation 1-2 (removed copper). 8300 ppm by weight of sulfuric acid was added while stirring, and the pH was adjusted to 4 to obtain a treatment solution 2. < Operation 5-4 '> (Removal (copper) in step (c)) Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 2 Add sodium hydroxide aqueous solution (sodium hydroxide 23 00 ppm by weight) and stir 3 After minutes, let stand for 20 minutes and filter. The pΗ of the upper solution was 10 '. The metal concentration was 3.3 ppm for copper and 10 ppm by weight for molybdenum. < Operation 5_4 > (Removal of metal (molybdenum) in step (c)) For the above-mentioned < operation 5-4, >, the clarified solution obtained was performed and implemented except that the amount of the agent ③ was changed to 1 000 ppm. ≪ Operation 1_4 > of Example 1 to obtain a final treatment solution. The final treatment liquid is colorless and transparent, and the metal concentration is copper 2.〇ρρηι The paper size is applicable to Chinese National Standard (CNS) A4 specifications (210X297 mm) -17- 200300406 A7 B7 V. Description of the invention (4) Molybdenum 1.7 ppm by weight . Details are shown in Table 1. (Please read the precautions on the back before filling this page) Comparative Example 3 < Operation 6-l > (Removal of solid content in step (a)) Using the same wastewater as in Example, a treatment liquid 1 was obtained in the same manner as in Example 1. The treatment liquid 1 had only a slight transparent blue color. The metal concentration of the treatment liquid 1 was 15 ppm by weight of copper and 10 ppm by weight of molybdenum. < operation 6-2 > (removal (copper)) To the treatment liquid 1 obtained in the above < operation 6_1 >, 30 wt ppm of a precipitating agent (agent ②) was added, and after stirring for 5 minutes, 4 wt ppm of a coagulant was added. (Pharmaceutical ①), after stirring for 3 minutes, let stand for 3 minutes. All solids (visual) are condensed, settled and filtered. The obtained treatment liquid was colorless and transparent. The metal concentration was 0.1 ppm by weight of copper, and 10 ppm by weight based on the mesh. < Operation 6-4 > (Removal of metal (molybdenum) in step (c)) The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed the above-mentioned liquid clarified solution obtained from the above < operation 6-3 > Instead of 1000 ppm, < operation 1-4 > was performed with Example 1 to obtain a final treatment solution. The final treatment solution was colorless and transparent, with a metal concentration of 0.1 ppm copper and 2.0 molybdenum p p m. Details are shown in Table 1. This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) -18- 200300406 A7 B7 V. Description of invention () | 5 Printed and removed (molybdenum) metal E E d by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs § : E product § Inch 〇_ • · · Q. Θ 0 ^ Advise: V 潞 潞 骠 Ε Ε § = Ε & Ε II §: S § 10 inch people CO · * ·· α: ·· CD © @ τ- 观 1 S wins · Hold five suspicions 骠 α. σ > ο ε & Ε ™ g 〇: Ε ° ^ §: © @ d 髁 骠 髁 骠 Ε Q. Ε ^ α. Q. C ΠΠ I it S §: © @ ^ SS · _ 鄹 booth 1 1 ° · E ^ Q. ^ E ° · E ·· & 8 ai § s-1 0〇 ·· *＊; •• ❺ @ CM Viewing s · · E E ε cm α. ^ E ttn O Q. § ^ E '" " < inch 〇 • · · · Θ Θ ^ Remove (copper) metal 1 | Q. § 蓼 〇〇Ε Q. 噚 〇 ^ 2 CM * Secret "" Obstruct Q · Xinjiang IIEE! §:-§ Cui CNJ E Q. rS !. ^ CO ^ 2 CO secret " ··· Tibet! Decarbonated E Q. 〇UO 8i 〇. E 〇. 〇1〇k 1 Ε Q- 〇1 m 1 ig ξ. IE g 〇S ml 1 Remove Copper Ε g Ιΐ! CO inch g ® Θ ds 蘅 ·· 鄹 欢 骠 1 1 1 2 α. C ·· 1 '^ inch Ε • · ο. ® ㊀CM view g · _ 厳 欢 骠 1 1 ^ Q. ρ ·· 1 af r inch Ε .. ♦ · Cl ❾㊀C \ JS g _ · Fiber earning 骠 1 ε ο. Ο! Ιi i " 1 ® θ d s s _ · Fiber reed removing solid content Ε Q. Ο τ— Ε ππ 8 = f θ 蘅 Excitation 骠 Q. Ο τ— Title Ε ο. 1 zone Ε S zone Η ns drive Μ 鄯 1 Ε α. ο ππ § = f 7 g = θ ί S Ε骠 i Series IK CM Study IK ¢ 0 Unveiled ί 镒 i5 CM i3 CO 镒 (Please read the precautions on the back before filling this page) This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -19 -200300406 A7 ___ B7 V. Description of the invention (6, Commercial use field According to the present invention, the waste liquid produced by the acrylic acid manufacturing process is treated by wet combustion and wet oxidation, and the metals in the wastewater generated can be effectively used. Except for the diagram, a brief description of Figure 1 This is a morphological system diagram of the implementation of the method for removing metals from waste water according to the present invention. Comparison of main components Table 1 Wet combustion device 2 Condensing agent 1 3 Precipitation tank 1 4 Precipitant 2 5 Condensing agent 2 6 Precipitation tank 2 7 Acid 8 Dehydration Carbonic acid 9 Precipitant 3 10 Coagulant 3 11 Precipitation tank 3 12 Centrifuge or filter press 13 Solid content 14 Process steps and then step by step This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the back first Please pay attention to this page and fill in this page)-Installed · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-20- 200300406 A7 B7 V. Invention Description (, Ί 15 Drainage (Please read the precautions on the back before filling this page)- Binding · Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives This paper is printed in accordance with Chinese National Standard (CNS) Α4 (210 × 297 mm) -21-